WO2017195828A1 - Dispersion aqueuse, film de revêtement, et stratifié - Google Patents

Dispersion aqueuse, film de revêtement, et stratifié Download PDF

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Publication number
WO2017195828A1
WO2017195828A1 PCT/JP2017/017693 JP2017017693W WO2017195828A1 WO 2017195828 A1 WO2017195828 A1 WO 2017195828A1 JP 2017017693 W JP2017017693 W JP 2017017693W WO 2017195828 A1 WO2017195828 A1 WO 2017195828A1
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polyolefin
aqueous dispersion
component
unsaturated carboxylic
mass
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PCT/JP2017/017693
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English (en)
Japanese (ja)
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中島　秀人
順次 森本
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住友化学株式会社
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Priority to KR1020187032972A priority Critical patent/KR102315744B1/ko
Priority to JP2018517057A priority patent/JP6936794B2/ja
Priority to US16/300,146 priority patent/US11149162B2/en
Priority to CN201780029393.0A priority patent/CN109071913B/zh
Priority to EP17796188.5A priority patent/EP3456780A4/fr
Publication of WO2017195828A1 publication Critical patent/WO2017195828A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/145—Copolymers of propene with monomers having more than one C=C double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to an aqueous dispersion, a coating film and a laminate.
  • polyolefins such as propylene homopolymers and copolymers of propylene and ⁇ -olefins have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., and are inexpensive, so home appliances, automobile parts, etc. It is used in a wide range of fields.
  • the surface of a substrate made of polyolefin is non-polar and has low adhesion to substances other than polyolefin, so it is difficult to form a coating film such as an adhesive or paint on the surface of a substrate made of polyolefin.
  • the base material formed from such a polyolefin may be subjected to surface coating in order to improve the susceptibility of the surface or improve the adhesion to a metal member, for example.
  • Patent Document 1 describes a composition containing a resin obtained by modifying a non-crystalline polypropylene resin with maleic anhydride
  • Patent Document 2 describes A composition (resin dispersion) containing a polymer in which a hydrophilic polymer or an acidic group is bonded to a propylene- ⁇ -olefin copolymer is described.
  • Patent Document 3 and Patent Document 4 describe compositions using a combination of a plurality of modified polyolefins.
  • the composition containing the modified polyolefin as described above includes an organic solvent composition used by dissolving the modified polyolefin in an organic solvent, and an aqueous dispersion composition (aqueous dispersion) used by dispersing the modified polyolefin in water. Also called). From the viewpoint of reducing the burden on the environment, it is desirable to use an aqueous dispersion composition.
  • the water-dispersed composition is more adhesive than the organic solvent-based composition in terms of adhesion to such a base material. May be inferior.
  • an aqueous dispersion composition there is a problem that the dispersibility of the modified polyolefin in water is not always good. Therefore, for example, modified polyolefins applicable to organic solvent-based compositions and modified polyolefins suitable for water-dispersed compositions that can be suitably dispersed in water cannot be diverted directly to water-dispersed compositions. And the composition needs to be considered separately.
  • a composition containing a conventional modified polyolefin has adhesiveness to a base material made of polyolefin, and other base materials (
  • a base material made of polyolefin and other base materials
  • the present invention provides an aqueous dispersion capable of forming a coating film that is compatible with adhesion to a substrate made of polyolefin and adhesion to other substrate (particularly a substrate having a polar surface) and also has excellent water resistance. It aims at providing a laminated body provided with a body and a coating film, and this coating film.
  • the present invention provides the following [1] to [16].
  • [1] (A) Polyolefin (a) having a structural unit derived from ethylene and a structural unit derived from propylene and having a melting peak observed by differential scanning calorimetry is high due to ⁇ , ⁇ -unsaturated carboxylic acids.
  • a modified polyolefin and (B) a polyolefin (B-1) having a structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, and / or the polyolefin ( B-1) a low-modified polyolefin (B-2) of an ⁇ , ⁇ -unsaturated carboxylic acid and (C) a basic compound, and a mass ratio of the component (A) to the component (B) ( An aqueous dispersion having (A) / (B)) of 60/40 to 97.5 / 2.5.
  • the component (A) is a highly graft-modified polyolefin of the polyolefin (a) with ⁇ , ⁇ -unsaturated carboxylic acids
  • the component (B-2) is an ⁇ , ⁇ -unsaturated polyolefin (B-1).
  • the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to polyolefin (a) in component (A) is 2.
  • [4] The structure unit according to any one of [1] to [3], wherein the structural unit derived from ethylene in the polyolefin (a) is 5 to 30 mol% based on all structural units constituting the polyolefin (a).
  • Aqueous dispersion [5] The aqueous dispersion according to any one of [1] to [4], wherein the component (A) has a weight average molecular weight of 20,000 to 200,000.
  • [6] The aqueous dispersion according to any one of [1] to [5], wherein the melting point measured by differential scanning calorimetry of the component (A) is 110 ° C. or lower.
  • the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to polyolefin (B-1) in polyolefin (B-2) is 100 masses of polyolefin (B-2).
  • the component (C) is an organic amine compound.
  • a laminate comprising a substrate having a nonpolar surface and the coating film according to [12] or [13] laminated on the nonpolar surface of the substrate.
  • a coating film that is compatible with adhesion with a substrate made of polyolefin and adhesion with other substrate (particularly a substrate having a polar surface) and has excellent water resistance.
  • An aqueous dispersion and a coating film, and a laminate comprising the coating film can be provided.
  • the aqueous dispersion which concerns on this embodiment contains the following (A) component, (B) component, and (C) component.
  • Polyolefin (B) component polyolefin (B-1) having a structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, and / or the polyolefin (B -1) Low-modified polyolefins with ⁇ , ⁇ -unsaturated carboxylic acids (B-2)
  • the component (A) is a highly modified polyolefin of the polyolefin (a) with ⁇ , ⁇ -unsaturated carboxylic acids, and can be obtained by modifying the polyolefin (a) with ⁇ , ⁇ -unsaturated carboxylic acids.
  • the highly modified polyolefin means that the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to the polyolefin (a) is 2. It means a modified polyolefin that is 0 part by mass or more.
  • the modification with ⁇ , ⁇ -unsaturated carboxylic acids may be graft modification or copolymerization.
  • the component (A) is preferably a highly graft-modified polyolefin of the polyolefin (a) with ⁇ , ⁇ -unsaturated carboxylic acids.
  • the polyolefin (a) has at least a structural unit derived from ethylene and a structural unit derived from propylene.
  • the amount of the structural unit derived from ethylene is usually 5 to 30 mol%, preferably 5 to 20 mol%, more preferably 5 to 19 mol%, still more preferably based on the total structural units constituting the polyolefin (a). Is from 10 to 19 mol%, particularly preferably from 11 to 18 mol%, most preferably from 11 to 17 mol%.
  • the amount of the structural unit derived from propylene is usually 70 to 95 mol%, preferably 80 to 95 mol%, more preferably 81 to 95 mol%, still more preferably based on all structural units constituting the polyolefin (a). Is 81 to 90 mol%, particularly preferably 82 to 89 mol%, most preferably 83 to 89 mol%.
  • the polyolefin (a) may consist of only a structural unit derived from ethylene and a structural unit derived from propylene, and has other structural units in addition to the structural unit derived from ethylene and the structural unit derived from propylene. You may do it. Examples of other structural units include structural units derived from ⁇ -olefins having 4 to 20 carbon atoms, cyclic olefins, vinyl aromatic compounds, and polyene compounds.
  • Examples of the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene.
  • Linear ⁇ -olefins such as 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like.
  • cyclic olefin examples include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano--but
  • vinyl aromatic compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinyl naphthalene.
  • polyene compounds include conjugated polyene compounds and non-conjugated polyene compounds.
  • conjugated polyene compound include aliphatic conjugated polyene compounds such as linear aliphatic conjugated polyene compounds, branched aliphatic conjugated polyene compounds, and alicyclic conjugated polyene compounds.
  • non-conjugated polyene compound examples include an aliphatic non-conjugated polyene compound and an alicyclic non-conjugated polyene compound.
  • aromatic polyene compounds and the like are also exemplified as polyene compounds. These polyene compounds may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like.
  • Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples thereof include dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene.
  • Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3- Dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene, and the like.
  • Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethy
  • Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, and cyclohexadiene.
  • aromatic polyene compound examples include divinylbenzene and vinylisopropenylbenzene.
  • the total amount of the structural units derived from ethylene and the structural units derived from propylene is preferably 85 mol% based on the total structural units constituting the polyolefin (a). As mentioned above, More preferably, it is 91 mol% or more, More preferably, it is 96 mol% or more. In other words, the amount of other structural units is preferably 15 mol% or less, more preferably 9 mol% or less, and even more preferably 4 mol% or less, based on the total structural units constituting the polyolefin (a). .
  • Polyolefin (a) is a polymer in which a melting peak (hereinafter also simply referred to as “melting peak”) is observed by differential scanning calorimetry (DSC).
  • a melting peak is observed by differential scanning calorimetry (DSC)” means that a crystal melting peak having a crystal melting heat amount of 1 J / g or more is observed in a temperature range of ⁇ 100 to 200 ° C.
  • a crystallization peak having a heat of crystallization of 1 J / g or more is observed. Polymer.
  • the polyolefin (a) is produced using a known Ziegler-Natta type catalyst or a known single-site catalyst (metallocene, etc.), and is preferably a known single from the viewpoint of improving the heat resistance of the dried coating film of the aqueous dispersion. Manufactured using a site catalyst (metallocene, etc.).
  • ⁇ , ⁇ -unsaturated carboxylic acids for modifying polyolefin (a) include ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof.
  • Examples include ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, citraconic acid and the like; ⁇ , ⁇ -unsaturated carboxylic acid anhydrides such as anhydrous Maleic acid, itaconic anhydride, citraconic anhydride, etc .; ⁇ , ⁇ -unsaturated carboxylic acid esters such as methyl maleate, methyl itaconate, methyl citraconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth ) Acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth)
  • ⁇ , ⁇ -unsaturated carboxylic acids may be used in combination of two or more thereof.
  • the number of carbon atoms of the group represented by R in the ester moiety (—CO—O—R) of (meth) acrylate is preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more. Usually, it is 20 or less.
  • the number of carbon atoms of the group represented by R in the ester moiety is 4.
  • maleic acid and maleic anhydride are preferable, and maleic anhydride is more preferable.
  • acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid
  • acrylate and methacrylate are collectively referred to as (meth) acrylate.
  • the molar ratio between the two is preferably ⁇ , ⁇ -unsaturated carboxylic acid anhydride / ⁇ , ⁇ -unsaturated.
  • the method for producing the component (A) for example, a method in which the polyolefin (a) is melted and then modified by adding an ⁇ , ⁇ -unsaturated carboxylic acid, and the polyolefin (a) is used in a solvent such as toluene or xylene.
  • a method in which an ⁇ , ⁇ -unsaturated carboxylic acid is added and modified after being dissolved or suspended examples thereof include a method in which a raw material monomer of the polyolefin (a) is copolymerized with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • melt-kneading means conventionally known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed.
  • a means for melt kneading from the viewpoint that continuous production is possible and productivity is improved, a polyolefin (a), ⁇ , ⁇ -unsaturated carboxylic acid that has been sufficiently premixed in advance using a single-screw or twin-screw extruder is used.
  • a method in which the acids and radical initiator are supplied from the supply port of the extruder and kneaded is preferably used.
  • the polyolefin (a) As a method of modifying the polyolefin (a) by dissolving or suspending it in a solvent such as toluene or xylene and then adding an ⁇ , ⁇ -unsaturated carboxylic acid, the polyolefin (a), ⁇ , ⁇ -unsaturated carboxylic acids and radical initiators are appropriately charged in any order or simultaneously, and the polyolefin (a) is dissolved or suspended in a solvent, and is usually heated with ⁇ , ⁇ -unsaturated carboxylic acids. Examples of the method include denaturation.
  • Examples of the method of copolymerizing the raw material monomer of polyolefin (a) and ⁇ , ⁇ -unsaturated carboxylic acids include known methods such as radical polymerization. For example, after the raw material monomer is melted, polymerization may be performed by adding ⁇ , ⁇ -unsaturated carboxylic acids, or after the raw material monomer is dissolved in a solvent such as toluene, ⁇ , ⁇ -unsaturated carboxylic acids are used. May be added for polymerization.
  • the structural unit derived from the ⁇ , ⁇ -unsaturated carboxylic acid anhydride in component (A) is an anhydride group. (—CO—O—CO—) may be retained, the anhydride group may have a ring-opened structure, or both may be included.
  • the amount of the solvent used may be an amount that can dissolve or suspend the polyolefin (a).
  • the amount of the solvent used may be, for example, 5 to 1000 parts by mass, 1 to 300 parts by mass, or 1 to 100 parts by mass with respect to 100 parts by mass of the polyolefin (a).
  • the amount of the radical initiator added is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the polyolefin (a).
  • the addition amount is 0.1 parts by mass or more, the modification amount of the polyolefin (a) is ensured, and the aqueous dispersion tends to be easily handled without becoming too viscous, and the addition amount is 10 parts by mass.
  • the content of the unreacted radical initiator in the component (A) to be obtained is reduced, and the adhesiveness of the aqueous dispersion tends to be further improved.
  • the radical initiator is, for example, an organic peroxide, preferably an organic peroxide having a decomposition temperature of 50 to 160 ° C. with a half-life of 1 hour.
  • the decomposition temperature is 50 ° C. or higher, the amount of modification tends to be improved, and when the decomposition temperature is 160 ° C. or lower, the decomposition of the polyolefin (a) tends to be reduced.
  • These organic peroxides preferably have an action of extracting protons from the polyolefin (a) after decomposition and generation of radicals.
  • organic peroxide having a decomposition temperature of 50 to 160 ° C. with a half-life of 1 hour examples include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, and percarbonate compounds.
  • organic peroxides include dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicar.
  • the amount of ⁇ , ⁇ -unsaturated carboxylic acid added is, for example, 5 to 60 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyolefin (a).
  • the addition amount is 5 parts by mass or more, it is preferable in that a desired amount of modification to the polyolefin (a) is obtained, and the aqueous dispersion tends to be easy to handle without becoming too viscous.
  • the addition amount is 60 parts by mass or less, the content of unreacted ⁇ , ⁇ -unsaturated carboxylic acids in the obtained component (A) is reduced, and the adhesiveness of the aqueous dispersion tends to be further improved.
  • the structural unit derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to the polyolefin (a) has an acid anhydride group (—CO—O—CO—) in which a ring structure is retained.
  • the acid anhydride group may have a ring-opened group, or may have both an acid anhydride group in which the ring structure is retained and a group in which the acid anhydride group is ring-opened. .
  • the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to the polyolefin (a) in the component (A) is preferably 2. 0 to 50 parts by weight, more preferably 2.0 to 40 parts by weight, still more preferably 2.0 to 30 parts by weight, still more preferably 2.0 to 15 parts by weight, particularly preferably 2.0 to 10 parts by weight. It is.
  • the weight average molecular weight (Mw) of the component (A) is preferably 20,000 to 200,000, preferably 25,000 to 150,000, more preferably 30,000 to 150,000.
  • Mw of the component (A) is 20000 or more, the adhesiveness of the aqueous dispersion is further improved, and when the Mw is 200000 or less, the particle size of the aqueous dispersion becomes small and the stability of the aqueous dispersion is excellent.
  • a weight average molecular weight (Mw), a weight average molecular weight (Mn), and molecular weight distribution (Mw / Mn) mean the standard polystyrene conversion value measured by gel permeation chromatography (GPC).
  • the melting point of the component (A) measured by differential scanning calorimetry (DSC) is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 90 ° C. or lower.
  • DSC differential scanning calorimetry
  • the component (A) may be a modified polyolefin obtained by further modifying the above highly modified polyolefin with ⁇ , ⁇ -unsaturated carboxylic acids with chlorine.
  • Chlorine modification is performed, for example, by dissolving a highly modified polyolefin of the above-described ⁇ , ⁇ -unsaturated carboxylic acids in a chlorinated solvent and irradiating with ultraviolet rays or in the presence of a catalyst containing a peroxide such as benzoyl peroxide.
  • the reaction is carried out by blowing chlorine gas under a normal pressure or under pressure in a solution state or in a non-uniform dispersion state.
  • the component (B) is at least one selected from the following polyolefin (B-1) and low-modified polyolefin (B-2).
  • Polyolefin (B-1) (unmodified) polyolefin low-modified polyolefin having a structural unit derived from at least one olefin selected from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms
  • B-2) polyolefin ( B-1)
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, And linear ⁇ -olefins such as -dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and the like.
  • the polyolefin (B-1) may consist only of a structural unit derived from at least one olefin selected from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms. In addition to structural units derived from olefins selected from olefins, they may have other structural units. Examples of other structural units include structural units derived from cyclic olefins, vinyl aromatic compounds, and polyene compounds. As the cyclic olefin, vinyl aromatic compound, and polyene compound, the same compounds as the cyclic olefin, vinyl aromatic compound, and polyene compound described in the above component (A) are used.
  • the amount of structural units derived from olefins selected from ethylene and ⁇ -olefins having 3 to 20 carbon atoms is the total structure constituting the polyolefin (B-1). Based on the unit, it is preferably at least 72 mol%, more preferably at least 81 mol%, still more preferably at least 96 mol%. In other words, the amount of other structural units is preferably 28 mol% or less, more preferably 19 mol% or less, and even more preferably 4 mol% or less, based on the total structural units constituting the polyolefin (B-1). It is.
  • the polyolefin (B-1) may be a polymer in which a melting peak is observed by differential scanning calorimetry (DSC), or may be a polymer in which the melting peak is not substantially observed.
  • DSC differential scanning calorimetry
  • the fact that a melting peak is observed has the same meaning as described for the component (A). “A melting peak is not substantially observed” means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in a temperature range of ⁇ 100 to 200 ° C.
  • Polyolefin (B-1) is a polymer in which a melting peak is preferably observed from the viewpoint of water resistance of the dried coating film of the aqueous dispersion.
  • the polyolefin (B-1) is preferably a polymer in which a melting peak is not substantially observed from the viewpoint of excellent adhesiveness and further excellent adhesion of the aqueous dispersion. More preferably, the polyolefin (B-1) has both a crystal melting peak with a heat of crystal melting of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more in a temperature range of ⁇ 100 to 200 ° C. Is a polymer in which is not observed.
  • the polyolefin (B-1) is produced using a known Ziegler-Natta type catalyst or a known single-site catalyst (metallocene, etc.), and is preferably a known single-site catalyst from the viewpoint of increasing the heat resistance of the aqueous dispersion. Manufactured using (metallocene, etc.). Polyolefin (B-1) is a polymer not modified with ⁇ , ⁇ -unsaturated carboxylic acids.
  • Polyolefin (B-2) is a low-modified polyolefin of polyolefin (B-1) with ⁇ , ⁇ -unsaturated carboxylic acids.
  • polyolefin (B-1) By modifying polyolefin (B-1) with ⁇ , ⁇ -unsaturated carboxylic acids, can get.
  • the low-modified polyolefin means that the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to the polyolefin (B-1) is 100 parts by mass of the polyolefin (B-2).
  • the modified polyolefin which is less than 2.0 mass parts is meant.
  • the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to the polyolefin (B-1) is preferably 0.0 mass by mass with respect to 100 mass parts of the polyolefin (B-2). Is 1.0 part by mass or less.
  • the low-modified polyolefin is preferably a low-graft modified polyolefin.
  • the ⁇ , ⁇ -unsaturated carboxylic acids for modifying the polyolefin (B-1) the ⁇ , ⁇ -unsaturated carboxylic acids described for the component (A) are used.
  • polyolefin (B-2) As a method for producing the polyolefin (B-2), a production method in which the polyolefin (a) is replaced with the polyolefin (B-1) in the production method described for the component (A) is used.
  • the amount of ⁇ , ⁇ -unsaturated carboxylic acid added is, for example, 0.001 to 5 parts by mass, preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of polyolefin (B-1).
  • the structural unit derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to polyolefin (B-1) has an acid anhydride group (—CO—O—CO—) in which a ring structure is retained.
  • the acid anhydride group may have a ring-opened group, and both the acid anhydride group in which the ring structure is retained and the acid anhydride group have a ring-opened group. Also good.
  • the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to (B-1) is preferably 0.001 part by mass with respect to 100 parts by mass of polyolefin (B-2). It is more than 2.0 parts by mass, more preferably 0.001 to 1.8 parts by mass, and still more preferably 0.001 to 1.5 parts by mass.
  • the weight average molecular weight (Mw) of the component (B) is preferably 5000 to 450,000, preferably 15000 to 350,000, more preferably 25000 to 250,000.
  • Mw of the component (B) is 5000 or more, the adhesiveness of the aqueous dispersion is further improved, and when the Mw is 450,000 or less, the aqueous dispersion does not become too viscous and the handling becomes easy.
  • the melting point measured by differential scanning calorimetry is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. It is as follows. When the melting point is 130 ° C. or lower, the heat treatment temperature in the bonding step can be lowered, and the process can save energy.
  • component (C) a compound capable of neutralizing the carboxyl group present in the aqueous dispersion is used.
  • (C) component may be ammonia, an organic amine compound, a metal hydroxide etc., for example, Preferably it is ammonia or an organic amine compound, More preferably, it is an organic amine compound whose boiling point is 200 degrees C or less. When using an organic amine compound having a boiling point of 200 ° C. or less, it can be easily volatilized by ordinary drying, and when forming a coating film using an aqueous dispersion, the water resistance and alkali resistance of the coating film are maintained or Can be improved.
  • Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like. Among these, the organic amine compound is preferably N, N-dimethylethanolamine.
  • Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.
  • the content of the component (C) is, for example, 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 2 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 10 parts by mass.
  • content of said each component means the total amount of 2 or more types of components.
  • the mass ratio ((A) / (B)) between the component (A) and the component (B) is preferably 60/40 or more, more preferably 65/35 or more, from the viewpoint of excellent adhesion of the aqueous dispersion. More preferably, it is 80/20 or more.
  • the mass ratio ((A) / (B)) between the component (A) and the component (B) is, for example, 97.5 / 2.5 or less, 95/5 or less, or 92.5 / 7.5 or less. It may be.
  • the mass ratio of the component (A) to the component (B) is preferably 60/40 to 97.5 / 2.5, more preferably 65/35 to 95/5, The ratio is preferably 70/30 to 92.5 / 7.5.
  • the aqueous dispersion containing the component (A), the component (B), and the component (C) can be prepared by a method known in the art, for example, after the resin to be emulsified is produced, and then the resin is dispersed in an aqueous medium. It can be produced using a method (for example, forced emulsification method, self-emulsification method, phase inversion emulsification method, etc.).
  • a method for example, forced emulsification method, self-emulsification method, phase inversion emulsification method, etc.
  • the two obtained dispersions are prepared.
  • the components (A) and (B) may be mixed in advance and then dispersed in an aqueous medium. It is preferable that the component (A) and the component (B) are mixed in advance and then dispersed in an aqueous medium.
  • a method of preparing an aqueous dispersion by preparing a mixture of a resin to be emulsified and water and a solvent other than water in a reactor, and then removing the solvent other than water from the mixture.
  • the heating can be performed, for example, at 50 to 200 ° C., preferably 60 to 150 ° C., more preferably 70 to 100 ° C.
  • the rotation speed of the stirrer can be set at, for example, about 50 to 16000 rpm.
  • each resin In the production of each resin, emulsion polymerization or suspension polymerization can be used. In this case, an aqueous dispersion can be obtained simultaneously with the production of the resin.
  • a container preferably sealed and / or sealed
  • a heating device capable of being heated
  • a stirrer capable of applying a shearing force or the like to the contents.
  • Pressure vessel is used as the reactor.
  • examples of the kneader include a roll mill, a kneader, an extruder, an ink roll, and a Banbury mixer.
  • an extruder or a multi-screw extruder having one or more screws in the casing may be used.
  • a resin to be emulsified and an emulsifier are mixed, and this is continuously supplied from a hopper or supply port of the extruder, and this is heated and melt-kneaded, and further, a compression zone of the extruder, Water is supplied from at least one supply port provided in the measuring zone, the deaeration zone, and the like, kneaded with a screw, and then continuously extruded from a die.
  • the water content in the aqueous dispersion is, for example, 30 to 97% by mass, preferably 35 to 95% by mass, more preferably 40 to 93% by mass, and still more preferably 45 to 90% by mass, based on the total amount of the aqueous dispersion. It is.
  • solvent other than water examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and methylene chloride.
  • Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene
  • esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone and cyclohexanone
  • methanol Ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol
  • alcohols such as ethylene glycol, propylene glycol, butanediol, dipropyl ether, dibutyl Ethers such as ether and tetrahydrofuran
  • organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropan
  • the solvent other than water is preferably a solvent that dissolves 1% by mass or more in water, more preferably a solvent that dissolves 5% by mass or more in water.
  • a solvent that dissolves 1% by mass or more in water more preferably a solvent that dissolves 5% by mass or more in water.
  • the ratio of the solvent other than water to water in the aqueous dispersion is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0. % By mass.
  • the volume-based average particle size of the dispersoid in the aqueous dispersion is preferably 2 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.5 ⁇ m or less.
  • the lower limit of the average particle size of the dispersoid of the aqueous dispersion is not particularly limited, but is, for example, 0.001 ⁇ m or more or 0.01 ⁇ m or more. When the average particle size is 2 ⁇ m or less, the stability of the aqueous dispersion is good, and the coating property to the substrate is also good.
  • the volume-based average particle size of the dispersoid is a particle size corresponding to a value of 50% of the cumulative particle size distribution on the volume basis, and is measured by, for example, a particle size distribution measuring device.
  • the ratio of the dispersoid having a particle diameter of 2 ⁇ m or more in the total dispersoid is preferably 5% or less, more preferably Is 3% or less, more preferably 1% or less.
  • the proportion is 5% or less, the stability of the aqueous dispersion is good, and the coating property to the substrate is also good.
  • ком ⁇ онент (A) and component (B) in addition to the resin (component (A) and component (B)), water and a solvent other than water, additional resin (resin other than component (A) and component (B)), emulsifier, Arbitrary components such as thickeners, dispersants, curing agents, pigments, viscosity modifiers, antifoaming agents, and further solvents can be added in appropriate amounts at any time. These components can also be added after mixing the component (A) and the component (B).
  • Further resins include, for example, polyolefin resins of a different type from the components (A) and (B), acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyacetic acid.
  • acrylic resins PMMA
  • PVC polyvinyl chloride
  • PS polystyrene
  • examples include various polymers and copolymers such as vinyl (PVAc), polytetrafluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), AS resin, and modified products thereof. These are used alone or in combination of two or more.
  • an adhesive resin or a resin that exhibits a function as a tackifier may be used.
  • resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, indene resins, polyurethane resins, and the like.
  • Rosins such as fluorides; terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, terpene hydrogenated resins, and other terpene resins; C5 petroleum fractions And petroleum resins polymerized from petroleum fractions having 9 carbon atoms and hydrogenated resins thereof; petroleum resins such as maleic acid modified products and fumaric acid modified products.
  • the aqueous dispersion may contain an emulsifier such as a nonionic emulsifier, an anionic emulsifier, a cationic emulsifier, an amphoteric emulsifier or the like as an emulsifier. Even if not, the dispersibility can be suitably maintained.
  • “Contains substantially no emulsifier” means that the content of the emulsifier is less than the effective amount necessary for imparting an emulsifying action to the aqueous dispersion. Specifically, the content of the emulsifier may be less than 20% by mass, less than 15% by mass, or less than 10% by mass based on the total amount of the components (A) and (B), and 0% by mass. It may be. You may use an emulsifier individually by 1 type or in combination of 2 or more types.
  • anionic emulsifiers include sulfate esters of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. And the like.
  • cationic emulsifiers examples include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt , Allyl trialkyl ammonium salt, diallyl dialkyl ammonium salt and the like.
  • alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt
  • alkylpyridium salts such as cetylpyridium salt and decylpyridium salt
  • oxyalkylenetrialkylammonium salt dioxyalkylenedialkylammonium salt
  • Allyl trialkyl ammonium salt diallyl dialkyl ammonium salt and the like.
  • nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, and ethylene oxide.
  • polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, and ethylene oxide.
  • -A compound having a polyoxyethylene structure such as a propylene oxide copolymer or a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester.
  • amphoteric emulsifiers examples include lauryl betaine and lauryl dimethylamine oxide.
  • Thickener is used to adjust the viscosity of the aqueous dispersion.
  • a thickener manufactured by ADEKA Corporation; Adecanol UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH- 541VF, UH-550, UH-752, H-756VF, manufactured by San Nopco; SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A- 818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050 and the like.
  • Dispersant is used to improve wettability to coated substrate.
  • a dispersant manufactured by ADEKA Corporation; Adeka Coal W-193, W-287, W-288, W-304, manufactured by BYK; BYK-333, BYK-345, BYK-346, BYK-347, BYK- 348, BYK-349, BYK-378, manufactured by San Nopco; Nopco wet 50, SN wet 366, Nopco 38-C, SN disperse sand 5468, 5034, 5027, 5040, 5020 and the like.
  • isocyanate type and / or carbodiimide type curing agents are used.
  • Examples of the carbodiimide-based curing agent include a carbodilite series (manufactured by Nisshinbo Chemical Co., Ltd.).
  • the content of the curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).
  • the curing agent may be added after being dissolved in an organic solvent.
  • the pigment examples include inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, perinone pigments, perylene pigments, and quinacridone pigments.
  • inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, perinone pigments, perylene pigments, and quinacridone pigments.
  • Color pigments such as organic pigments such as pigments, isoindolinone pigments, indigo pigments, phthalocyanine pigments; extender pigments such as talc, calcium carbonate, clay, kaolin, silica, precipitated barium sulfate; conductive carbon, antimony-doped Examples include conductive pigments such as whiskers coated with tin oxide; non-colored or colored metallic luster such as metals or alloys such as aluminum, copper, zinc, nickel, tin, and aluminum oxide. A pigment is used individually by 1 type or in combination of 2 or more types.
  • a pigment dispersant may be used in combination.
  • the pigment dispersant include an aqueous acrylic resin such as Jonkrill manufactured by BASF Japan; an acidic block copolymer such as BYK-190 manufactured by BYK; a styrene-maleic acid copolymer; Air Products (air product) Acetylenic diol derivatives such as Surfynol T324 manufactured by Yokogawa Chemical Co .; and water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Co., Ltd.
  • a pigment paste in which pigment dispersion is stable can be prepared.
  • the viscosity modifier is an agent added to properly adjust the viscosity of the aqueous dispersion, and is used within a range that does not significantly deteriorate the performance of the aqueous dispersion of the present invention.
  • examples of the viscosity modifier are not particularly limited, and examples thereof include BYK-420 and BYK-425 (manufactured by BYK).
  • Aqueous dispersions are phenol stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, anti-settling agents, as needed, as long as the desired properties are not impaired.
  • Stabilizers such as antioxidants, heat stabilizers, light stabilizers; thixotropic agents, thickeners, dispersants, antifoaming agents, weathering agents, antistatic agents, lubricants, nucleating agents, flame retardants, oil agents, dyes ,
  • Additives such as curing agent, crosslinking agent; glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, finely divided silica, mica, It may further contain optional components such as inorganic and organic fillers such as calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, and celite. .
  • the aqueous dispersion according to the present embodiment includes polyethylene (a polyolefin having a structural unit derived from ethylene as a main component), polypropylene (a polyolefin having a structural unit derived from propylene as a main component), and polystyrene (a structural unit derived from styrene). It is preferably used for a substrate made of such a polyolefin.
  • the aqueous dispersion according to this embodiment has excellent adhesion to other base materials other than the base material made of polyolefin.
  • Other base materials include, for example, acrylic urethane resin, polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, vinyl chloride resin, polyester resin, polyurethane resin, epoxy resin, paper, synthetic paper, wood, woven Widely and generally formed of cloth, knitted fabric, non-woven fabric, metal components (including iron, aluminum, copper, nickel, silver, gold, platinum, various alloys, etc.), wood (including pulp, paper, etc.), stone, etc.
  • the aqueous dispersion according to the present embodiment is excellent in both adhesion with a substrate having a nonpolar surface such as a substrate made of polyolefin, and adhesion with a substrate having a polar surface.
  • a substrate having a nonpolar surface such as a substrate made of polyolefin
  • adhesion with a substrate having a polar surface for example, it is suitable as an adhesive for adhering a base material made of polyolefin (a base material having a nonpolar surface) and a base material having a polar surface to each other. That is, the aqueous dispersion exhibits excellent adhesiveness even when substrates made of the same kind of material are bonded to each other or when substrates made of different materials are bonded together.
  • the aqueous dispersion is particularly suitable for adhesion between a polyurethane resin film and a polyolefin resin film, adhesion between a polyurethane resin film and a polyester resin film, lamination of a polyurethane resin film and a metal, and the like. Therefore, the aqueous dispersion according to the present embodiment is useful for various applications, and can be used, for example, as it is as an aqueous adhesive or primer composition, or as an aqueous coating composition, aqueous adhesive or primer composition. It can be used together with other components in the product.
  • Examples of the other components include an aqueous dispersion of an epoxy resin, an aqueous dispersion of a polyester, an aqueous dispersion of an acrylic resin (acrylic dispersion), and an aqueous dispersion of a urethane resin (polyurethane dispersion). .
  • the aqueous coating composition is applied to a substrate and, for example, at a temperature of 40 ° C. to 160 ° C., preferably 60 ° C. to 130 ° C., more preferably 80 ° C. to 110 ° C.
  • a coating film can be formed on the substrate by heating for 1 hour, preferably 3 to 30 minutes.
  • the primer composition after forming a coating film of the primer composition by drying and curing at a temperature of room temperature (for example, 25 ° C.) to 100 ° C., if necessary, another paint or the like is applied on the coating film. For example, it is applied by heating at a temperature of 40 ° C. to 160 ° C., preferably 60 ° C. to 130 ° C., more preferably 80 ° C. to 110 ° C., for example, for 1 minute to 1 hour, preferably 3 minutes to 30 minutes.
  • a paint film can be formed.
  • paints include colored base paints and clear paints. These may be aqueous or organic solvent-based, and may contain various resins such as olefin polymers and various pigments.
  • the aqueous adhesive is applied to one or both surfaces of the substrate, dried and cured at a temperature of room temperature (for example, 25 ° C.) to 100 ° C., if necessary, and then the two substrates.
  • a base material can be adhere
  • the shape of the substrate is not particularly limited and may be a film, a sheet, a plate-like body, or the like, or a molding obtained by a known molding method such as injection molding, compression molding, hollow molding, extrusion molding, or rotational molding. It may be a body.
  • the base material may be composed of a resin composition containing the resin and an inorganic filler component, a pigment, and the like.
  • inorganic filler components and pigments include plate-like fillers such as talc, mica, and montmorillonite; fibrous fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, and zonolite; Acicular (whisker) fillers such as potassium titanate, magnesium oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate And particulate fillers such as magnesium carbonate; balun fillers such as glass balloons; and inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate.
  • plate-like fillers such as talc, mica, and montmorillonite
  • fibrous fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, and zonolite
  • the method for applying the aqueous dispersion mixture to the substrate is not particularly limited, and any known method can be used.
  • air spray method airless spray method, gravure roll coating, reverse roll coating, wire bar
  • coating lip coating, air knife coating, curtain flow coating, spray coating, dip coating, and brush coating.
  • Drying, curing, and heating can be performed using, for example, nichrome wire, infrared rays, high frequency, and the like, for example, using a conventionally used method and apparatus.
  • the coating film which concerns on this embodiment is a coating film formed from the aqueous dispersion mentioned above.
  • the coating film which concerns on this embodiment contains the following (A) component, (B) component, and (C) component.
  • Polyolefin (B) component polyolefin (B-1) having a structural unit derived from one or more olefins selected from the group consisting of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, and / or the polyolefin (B -1) Low-modified polyolefins with ⁇ , ⁇ -unsaturated carboxylic acids (B-2)
  • the thickness of the coating film to be formed is appropriately selected depending on the material and shape of the base material, the composition of the paint used, etc., for example, 0.1 ⁇ m to 500 ⁇ m, preferably 1 ⁇ m to 300 ⁇ m, more preferably 3 ⁇ m to 200 ⁇ m. .
  • the laminated body which concerns on one Embodiment is equipped with the base material which has a nonpolar surface, and the said coating film laminated
  • the laminate may further include a substrate having a polar surface laminated on a surface opposite to the substrate having a nonpolar surface of the coating film. That is, the laminated body which concerns on other one Embodiment is a laminated body by which the base material which has a nonpolar surface, the said coating film, and the base material which has a polar surface are laminated
  • the coating film, laminate and coated article using the aqueous dispersion according to the present embodiment have excellent water resistance and moisture resistance, and therefore can be used for various industrial parts such as automobiles, home appliances and building materials. It has sufficient performance for practical use as a thin-walled, highly functional, and large-sized component / material.
  • Such coatings, laminates and coated articles are, for example, automobile parts such as bumpers, instrument panels, trims, garnishes, television cases, washing machine tanks, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, It can be used as a molding material for various industrial parts such as toiletry parts such as toilet seat lids and water tanks, bathroom parts such as bathtubs, bathroom walls, ceilings, and drain pans.
  • modified functional group units (1) Quantification of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids chemically bonded to polyolefin resins (hereinafter also referred to as “modified functional group units”) The amount of modified functional group units in graft-modified polyolefin is In order to remove ⁇ , ⁇ -unsaturated carboxylic acids that are not bonded to the polyolefin resin, 1.0 g of a sample is dissolved in 20 ml of xylene, and the sample solution is dropped into 300 ml of methanol while stirring to reprecipitate the sample.
  • the obtained sample is hot-pressed to form a film having a thickness of 100 ⁇ m, and the infrared absorption spectrum of the obtained film was measured.
  • the quantity (mass%) of the modification functional group unit with respect to 100 mass parts of graft modification polyolefin it computed using the analytical curve created by measuring resin with modification amount by said method. For example, when maleic anhydride is quantified, it is quantified based on absorption around 1780 cm-1.
  • the average particle size of the dispersoid was measured using a dense particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd., which observes the scattered light from the particles using dynamic light scattering.
  • the amount of structural units derived from dodecyl methacrylate was 4.3% by mass.
  • maleic anhydride 4.3% by mass
  • dodecyl methacrylate 15.2% by mass.
  • aqueous dispersion (D-1).
  • the nonvolatile content was about 34%
  • the volume-based average particle size of the dispersoid in (D-1) was 0.08 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • aqueous dispersion (D-2).
  • the nonvolatile content was about 37%
  • the volume-based average particle size of the dispersoid in (D-2) was 0.08 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • aqueous dispersion (D-3).
  • the nonvolatile content was about 35%
  • the volume-based average particle size of the dispersoid in (D-3) was 0.8 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • aqueous dispersion (D-4).
  • the nonvolatile content was about 32%
  • the volume-based average particle size of the dispersoid in (D-4) was 0.2 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • Example 5 85 g of highly modified polyolefin (A-3) and 15 g of polyolefin (a-1) were put in a separable flask and melted in an oil bath maintained at 100 ° C., and then 40 g of 2-butanol and 10 g of dimethylaminoethanol were added. , Stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the content was taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-5).
  • the non-volatile content was about 35%, the volume-based average particle size of the dispersoid in (D-5) was 0.09 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • Example 6 80 g of highly modified polyolefin (A-3) and 20 g of polyolefin (a-1) were put in a separable flask and melted in an oil bath maintained at 100 ° C., and then 40 g of 2-butanol and 10 g of dimethylaminoethanol were added. , Stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-6).
  • the nonvolatile content was about 38%, the average particle size of the dispersoid in volume reference in (D-6) was 0.08 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • Example 7 75 g of highly modified polyolefin (A-3) and 25 g of polyolefin (a-1) were put in a separable flask and melted in an oil bath maintained at 100 ° C., and then 40 g of 2-butanol and 10 g of dimethylaminoethanol were added. , Stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-7).
  • the nonvolatile content was about 35%
  • the volume-based average particle size of the dispersoid in (D-7) was 0.10 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • Example 8 67.5 g of highly modified polyolefin (A-3) and 32.5 g of polyolefin (a-1) were put in a separable flask and melted in an oil bath maintained at 100 ° C., and then 40 g of 2-butanol and dimethylamino were dissolved. Ethanol 10g was added and stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-8).
  • the nonvolatile content was about 37%, the volume average particle size of the dispersoid in (D-8) was 0.11 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • aqueous dispersion (D-9).
  • the nonvolatile content was about 39%
  • the volume-based average particle size of the dispersoid in (D-9) was 0.08 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • Example 11 85 g of highly modified polyolefin (A-3) and 15 g of polyolefin (a-1) were put in a separable flask and melted in an oil bath maintained at 100 ° C., and then 40 g of 2-butanol and 10 g of dimethylaminoethanol were added. , Stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-11).
  • the nonvolatile content was about 30%, the volume-based average particle size of the dispersoid in (D-11) was 0.08 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • aqueous dispersion (D-12).
  • the nonvolatile content was about 30%
  • the volume-based average particle size of the dispersoid in (D-12) was 0.40 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • Example 13 85 g of high-modified polyolefin (A-3) and 15 g of low-modified polyolefin (B-2-1) were put in a separable flask and melted in an oil bath maintained at 100 ° C., and then 40 g of 2-butanol and dimethylamino Ethanol 10g was added and stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-13).
  • the non-volatile content was about 37%, the volume-based average particle size of the dispersoid in (D-13) was 0.09 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • ion exchange water at 80 ° C. was added little by little with vigorous stirring.
  • 250 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (D-14).
  • the nonvolatile content was about 39%, the volume-based average particle size of the dispersoid in (D-14) was 0.09 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • the nonvolatile content was about 34%, the volume-based average particle size of the dispersoid in (D-15) was 0.07 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • the nonvolatile content was about 30%, the volume-based average particle size of the dispersoid in (D-16) was 0.08 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • the non-volatile content was about 35%, the volume-based average particle size of the dispersoid in (D-17) was 0.07 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • the nonvolatile content was about 33%, the volume-based average particle size of the dispersoid in (D-18) was 0.07 ⁇ m, and the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • aqueous dispersion (D-20).
  • the nonvolatile content was about 30%
  • the volume-based average particle size of the dispersoid in (D-20) was 0.31 ⁇ m
  • the proportion of the dispersoid having a particle size of 2 ⁇ m or more in the total dispersoid was 0%.
  • ⁇ Preparation of test paint> Apply the aqueous dispersion prepared in each of the above Examples and Comparative Examples to a polypropylene substrate (degreased) with a wire bar to a dry film thickness of about 10 ⁇ m, and heat at 50 ° C. for 5 minutes. After drying, spray paint acrylic urethane paint "Polynal No. 800" (manufactured by Ohashi Chemical Industry Co., Ltd.) to a dry film thickness of about 100 ⁇ m, and heat dry at 80 ° C. for 30 minutes for testing. A painted product was prepared.
  • ⁇ Evaluation of water resistance> Apply the aqueous dispersion prepared in each of the above Examples and Comparative Examples to a polypropylene substrate (degreased) with a wire bar to a dry film thickness of about 10 ⁇ m, and heat at 50 ° C. for 5 minutes. It dried and then heat-dried at 80 degreeC for 30 minutes, and produced the test coating material. This test coating was immersed in warm water at 40 ° C. for 10 days, and it was visually confirmed whether or not the surface of the coating film was whitened by absorbing water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une dispersion aqueuse contenant : (A) une polyoléfine hautement modifiée obtenue, au moyen d'un acide carboxylique α,β-insaturé, à partir d'une polyoléfine (a) qui présente un motif structurel dérivé de l'éthylène et un motif structurel dérivé du propylène, et dans laquelle un pic de fusion est observé par calorimétrie différentielle à compensation de puissance ; (B) une polyoléfine (B-1) présentant un motif structurel dérivé d'une ou plusieurs oléfines sélectionnées dans le groupe constitué de l'éthylène et des α-oléfines ayant de 3 à 20 atomes de carbone, et/ou une polyoléfine peu modifiée (B-2) obtenue à partir de la polyoléfine (B-1) au moyen d'un acide carboxylique α,β-insaturé ; et (C) un composé alcalin, dans lequel le rapport en masse ((A)/(B)) entre le constituant (A) et le constituant (B) est de 60/40 à 97,5/2,5.
PCT/JP2017/017693 2016-05-13 2017-05-10 Dispersion aqueuse, film de revêtement, et stratifié WO2017195828A1 (fr)

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JP2018517057A JP6936794B2 (ja) 2016-05-13 2017-05-10 水性分散体、塗膜及び積層体
US16/300,146 US11149162B2 (en) 2016-05-13 2017-05-10 Aqueous dispersion, coating film, and laminate
CN201780029393.0A CN109071913B (zh) 2016-05-13 2017-05-10 水性分散体、涂膜及层叠体
EP17796188.5A EP3456780A4 (fr) 2016-05-13 2017-05-10 Dispersion aqueuse, film de revêtement, et stratifié

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WO2020044920A1 (fr) 2018-08-29 2020-03-05 住友化学株式会社 Dispersion aqueuse
US11180663B2 (en) * 2019-04-26 2021-11-23 Raytheon Technologies Corporation Color changing adhesive bond primer
WO2022244879A1 (fr) * 2021-05-20 2022-11-24 三井化学株式会社 Composition de résine, son utilisation et procédé pour sa production
WO2023008235A1 (fr) * 2021-07-30 2023-02-02 ユニチカ株式会社 Dispersion de résine de polyoléfine et son procédé de fabrication

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JP6751046B2 (ja) * 2017-03-29 2020-09-02 株式会社神戸製鋼所 ポリオレフィン接着用表面処理金属板、複合部材、及び複合部材の製造方法
EP3908461B1 (fr) * 2019-01-11 2024-08-14 Basf Se Procédé de revêtement par une feuille au moyen d'un système de cylindre de gravure
CN114634677B (zh) * 2020-12-16 2023-05-26 万华化学集团股份有限公司 一种水性分散体组合物及其制备方法和应用

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WO2020044920A1 (fr) 2018-08-29 2020-03-05 住友化学株式会社 Dispersion aqueuse
CN112639013A (zh) * 2018-08-29 2021-04-09 住友化学株式会社 水性分散体
JPWO2020044920A1 (ja) * 2018-08-29 2021-08-26 住友化学株式会社 水性分散体
EP3845592A4 (fr) * 2018-08-29 2022-05-25 Sumitomo Chemical Company Limited Dispersion aqueuse
JP7431737B2 (ja) 2018-08-29 2024-02-15 住友化学株式会社 水性分散体
US11180663B2 (en) * 2019-04-26 2021-11-23 Raytheon Technologies Corporation Color changing adhesive bond primer
WO2022244879A1 (fr) * 2021-05-20 2022-11-24 三井化学株式会社 Composition de résine, son utilisation et procédé pour sa production
WO2023008235A1 (fr) * 2021-07-30 2023-02-02 ユニチカ株式会社 Dispersion de résine de polyoléfine et son procédé de fabrication

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US20190177568A1 (en) 2019-06-13
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US11149162B2 (en) 2021-10-19
KR102315744B1 (ko) 2021-10-20
EP3456780A1 (fr) 2019-03-20
CN109071913B (zh) 2021-03-30
CN109071913A (zh) 2018-12-21
EP3456780A4 (fr) 2020-02-12

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